CN1266814A - Hydrogen producer - Google Patents
Hydrogen producer Download PDFInfo
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- CN1266814A CN1266814A CN00104316.1A CN00104316A CN1266814A CN 1266814 A CN1266814 A CN 1266814A CN 00104316 A CN00104316 A CN 00104316A CN 1266814 A CN1266814 A CN 1266814A
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- C01B3/50—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification
- C01B3/56—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification by contacting with solids; Regeneration of used solids
- C01B3/58—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification by contacting with solids; Regeneration of used solids including a catalytic reaction
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- C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
- C01B3/34—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
- C01B3/48—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents followed by reaction of water vapour with carbon monoxide
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Abstract
A hydrogen generating apparatus having a fuel feeding part, a water feeding part for fuel reforming, an oxidant gas feeding part, a reforming catalyst body, a heating part for the reforming catalyst, a CO shifting catalyst body and a CO purification catalyst body is provided wherein the reforming catalyst body, the CO shifting catalyst body and the CO purification catalyst body are sequentially ordered from the fuel feeding part toward the downstream side, and wherein a shifting catalyst of the shifting catalyst body contains as one component at least a platinum group-type catalyst. A fuel and water are fed to the reforming part which has been heated, and an oxidant gas from the oxidant gas feeding part is nixed with each of a reformed gas introduced into the shifting part and a shifted gas obtained in the shifting part and introduced into the purification part, wherein at least a part of the reformed gas and at least a part of the shifted gas are oxidized, respectively, in the shifting part and the purification part.
Description
The hydro carbons etc. that the present invention relates to act as a fuel is a raw material with water, fuel is carried out the water vapor modification and obtains the apparatus for forming hydrogen of hydrogen.
The method that makes fuel carry out the water vapor modification is a kind of of method for forming hydrogen.In this method, be raw material, partly make fuel generation water vapor modified-reaction and generate hydrogen in the modification that is provided with modified catalyst with fuel such as alcohols such as hydro carbons such as Sweet natural gas and LPG, methyl alcohol or petroleum naphtha and water.Because above-mentioned water vapor modified-reaction has also generated the carbon monoxide as byproduct, so, in the past all also with making water and carbon monoxide carry out the transform portion of shift reaction.
In addition, for giving fuel cell, particularly polymer electrolyte fuel cell to provide hydrogen and when using water vapor modification method, in order further removing through the carbon monoxide in the reformed gas of transform portion, to be provided with the purification part of utilizing carbon monoxide oxidation style or methanation method etc.Be provided with the catalyst for reaction corresponding to separately in aforementioned modification part, transform portion and the purification part respectively, because temperature of reaction is different because of the difference of catalyst system therefor, so, enough stably generate for making Hydrogen Energy, these catalyzer need be heated to temperature of reaction separately.
In the above-mentioned apparatus for forming hydrogen, owing to only partly be provided with hot spots in the modification that is positioned at the upstream, so the temperature of modification part is the highest, then, temperature reduces successively according to the purification part of the transform portion that flows into modified gas, inflow reformed gas.Therefore, adopted the heat with modification part, for example the waste heat of heat of possessing with modified gas or hot spots is successively to transform portion with purify the structure that part heats.
But the catalyst temperature of each reactive moieties in the said structure (modification part, transform portion and purification part) reaches stable needs the regular hour.Exactly, the apparatus for forming hydrogen based on continuous operation that uses owing to factory can be set and turn round start time, so there is not special problem.But, frequent for starting, and need the apparatus for forming hydrogen of stable at short notice generation hydrogen just not ideal.
At this situation, used to correspond respectively to modification part and the purification portion branch is provided with special-purpose hot spots, makes hot spots running when the catalyzer heating that device is started, thus the method for shortening start time.But existing owing to being assembled into hot spots in the device, this method make structure become complicated, the problem that simultaneously the device price is increased.
In view of the above fact, first purpose of the present invention provides in having set the apparatus for forming hydrogen that daily startup stops, and can make the catalyst temperature of each reactive moieties reach stable apparatus for forming hydrogen at short notice with simple structure.
When carrying out above-mentioned water vapor modification, the modification temperature of hydrocarbon fuel such as methane, propane, gasoline, kerosene is about 500～800 ℃, and the modification temperature of pure and mild ethers fuel is about 200～400 ℃.
At this moment, because the concentration at the carbon monoxide (CO) that pyroreaction produced is high more, particularly under the situation of using hydrocarbon fuel, for example be reduced to 0.1～1%, use the CO conversion catalyst to make CO and steam reaction for making CO concentration.
Particularly as polymer electrolyte fuel cell because be necessary will about 100 ℃ low temperature down the CO concentration of the fuel cell of work reduce to about several ppm, added air, and adopted and can make the CO CO cleaning catalyst of oxidation selectively.These catalyzer can be pellected catalyst bodies such as cylindric and spherical.
But, when using the pellected catalyst body and since fuel cell when starting at every turn thermal shocking and the vibration when vehicle-mounted can destroy catalyst body, so, need to replace new catalyst body, the problem that can not make full use of like this with regard to the original life that has catalyst component.And the catalyst fines that produces in the time of may also the catalyst body disintegration can taking place stops up the problem of the fuel channel of fuel cell.
Promptly, apparatus for forming hydrogen in the past is merely able to carry out steady running in the chemical plant, in not needing the purposes of frequent starting operation, do not have too big problem, start repeatedly and shut down, have the occasion of high vibration to go wrong but be used for automobile and this needs of housekeeping fuel cell.
In view of the above fact, second purpose of the present invention provides and promptly is used in and need starts repeatedly and shut down, and the occasion of high vibration is arranged, and the performance of catalyst body also can be given full play to, can utilize fully its work-ing life, for a long time the apparatus for forming hydrogen of steady operation.
Utilize above-mentioned water vapor modification to make to be provided with between modified catalyst body, CO conversion catalyst body and the CO cleaning catalyst body of traditional apparatus for forming hydrogen that hydrogen produces and prevent the device that disperses.
Be not provided with under the situation prevent the device that disperses, catalyst body was subjected to thermal shocking when apparatus for forming hydrogen was started, because of vibration makes catalyst body destroyed, if life-time service, the catalyst component that then comes off may disperse to the downstream side of catalyst body under automobile scenarios.
In this case, the modified catalyst that disperses makes the modified gas methanation, and the CO conversion catalyst that disperses has hindered the selective oxidation of CO, and because of the countertransference reaction increases CO concentration to some extent, this just becomes one of whole device working efficiency main reasons for decrease.
This only is applicable to regard to explanation method in the past and carries out steady running in the chemical plant, in the purposes that does not need frequent starting, there is not too big problem, start repeatedly and shut down but be used for this needs of automobile and housekeeping fuel cell, and have the occasion of high vibration many problems will occur.
In view of the above fact, but the 3rd purpose of the present invention is the apparatus for forming hydrogen of long-term stable operation that provides the catalyst-free body to disperse influence for the problem of eliminating aforementioned apparatus for forming hydrogen.
At first, for finishing purpose 1 of the present invention, the invention provides a kind of apparatus for forming hydrogen, this device possesses the part of the fuel supply, the fuel reforming water is supplied with part, oxidant gas supply part, modified catalyst body, aforementioned modified catalyst hot spots, CO conversion catalyst body and cleaning catalyst body, and modified catalyst body, CO conversion catalyst body and CO cleaning catalyst body begin downstream from aforementioned part of the fuel supply, and side sets gradually.The feature of this device is, partly provide fuel and water to aforementioned modification through heating, at the aforementioned modified gas that imports aforementioned transform portion, and obtain to import in the aforementioned reformed gas that purifies part in aforementioned transform portion and be mixed into the oxidant gas of supplying with part from aforementioned oxidant gas, make aforementioned modified gas and aforementioned reformed gas at least a portion in aforementioned transform portion and the aforementioned purification part oxidized.
Aforementioned part of the fuel supply and water supply are partly for being connected as a single entity, and the CO conversion catalyst is the catalyzer of the shift reaction of water and carbon monoxide.
In this case, preferably comprise platinum group catalyst in the conversion catalyst of aforementioned conversion catalyst body at least.
In addition, preferably have the conversion catalyst temperature measuring part that can measure aforementioned conversion catalyst body temperature degree, the oxidant gas amount that is mixed in the aforementioned modified gas by adjusting can be controlled the conversion catalyst temperature like this.
Again, preferably have the cleaning catalyst temperature measuring part that can measure aforementioned cleaning catalyst body temperature degree, the oxidant gas amount that is mixed in the aforementioned reformed gas by adjusting can be controlled the cleaning catalyst temperature like this.
Preferably make from being mixed into the oxidant gas of supplying with part from aforementioned oxidant gas in the fuel of aforementioned part of the fuel supply and water supply part and the water again.
Again, preferably have the modified catalyst temperature measuring part that can measure aforementioned modified catalyst body temperature degree, the oxidant gas amount that is mixed in aforementioned fuel and the water by adjusting can be controlled the modified catalyst temperature like this.
In order to finish above-mentioned purpose 2, the modified catalyst body in the apparatus for forming hydrogen of the present invention, CO conversion catalyst body and CO cleaning catalyst body preferably select for use the carrier with honeycomb structure, foam structure or ripple struction that is loaded with catalyst component to form.
Hydrocarbon fuel, Aalcohols fuel or ethers fuel can be provided by aforementioned part of the fuel supply.
In addition, aforementioned fuel reforming water is supplied with part water vapor and air can be provided simultaneously.
Again, aforementioned fuel reforming water is supplied with part and also can only be provided air.
The material that constitutes aforementioned bearer comprises heat-resistant inorganic material, metal and heat conductivity inorganic materials etc.In addition, aforementioned bearer also can be made of the matrix material that heat-resistant inorganic material and metal or heat conductivity inorganic materials are formed.
For achieving the above object 3, between aforementioned modified catalyst body in the apparatus for forming hydrogen of the present invention and aforementioned CO conversion catalyst body, and at least one place between aforementioned CO conversion catalyst body and CO cleaning catalyst body is provided with aforementioned anti-sputtering device.
Aforementioned anti-sputtering device is a kind of strainer, is preferably in the pressure-detecting device that aforementioned strainer upstream side and downstream side are provided with the pressure-losses that can detect aforementioned strainer.
Aforementioned strainer can be made of the fiber that metal, pottery or their complex body are formed.Mesh-shape, the cellular or foam shape strainer that also can use metal, pottery or their complex body to form.
In addition, the temperature of the aforementioned strainer in the apparatus for forming hydrogen of the present invention preferably is higher than the temperature that makes the modified gas methanation.
In addition, be preferably near temperature-detecting device being set on the position of aforementioned strainer.
Fig. 1 is the simple longitudinal diagram that the apparatus for forming hydrogen of the invention process state 1 constitutes.
Fig. 2 is the simple longitudinal diagram that the apparatus for forming hydrogen of the invention process state 2 constitutes.
Fig. 3 is the simple longitudinal diagram that the apparatus for forming hydrogen of the invention process state 3 constitutes.
Fig. 4 is the simple longitudinal diagram that the apparatus for forming hydrogen of comparative example 1 of the present invention constitutes.
Fig. 5 is the simple longitudinal diagram that the apparatus for forming hydrogen of the invention process state 4 constitutes.
Fig. 6 is the simple longitudinal diagram that the apparatus for forming hydrogen of the invention process state 5 constitutes.
For the ease of understanding, be representative with enforcement state shown in following, the present invention will be described with reference to the accompanying drawings.
At first, the enforcement state 1 to apparatus for forming hydrogen of the present invention describes.
Fig. 1 is the simple longitudinal diagram of the apparatus for forming hydrogen structure of the invention process state 1.Among Fig. 1, supply with the raw material supplying part 1 of part fuel and water such as hydro carbons as the raw material of water vapor modified-reaction are provided by having part of the fuel supply and fuel reforming water concurrently.
The modified catalyst part 2b that is provided with the modified catalyst body 2a that comprises the water vapor modified-reaction in the modification part 2 carries out the water vapor modification to fuel.Here, modified catalyst 2a can use catalyzer that for example is mixed with by the platinum family precious metal etc.
Modified catalyst temperature measuring part 3 can be measured the temperature that is carried on the modified catalyst 2a on the modified catalyst body 2b.The effect of hot spots 4 is when the water vapor modification of carrying out fuel modification partly to be heated, and used herein is flame burner.
Comprise conversion catalyst body 6a in the transform portion 6, make the carbon monoxide in the modified gas that modification part 2 obtains carry out shift reaction.In addition, also be provided with the conversion catalyst temperature measuring part 7 of the temperature that can detect conversion catalyst body 6a.The catalyzer on the conversion catalyst body 6a of being carried on has here for example used catalyzer that is mixed with by the platinum family precious metal or the catalyzer that contains copper at least.
The inside that purifies part 10 is provided with cleaning catalyst body 10a such as platinum family oxide catalyst, and the carbon monoxide in the reformed gas that transform portion 6 is obtained carries out oxidation and/or hydrogenation and reformed gas is purified.In addition, also be provided with cleaning catalyst temperature measuring part 11.
Be provided with raw material supplying passage 5 in raw material supplying part 1 and 2 of modification parts,, be provided with modified gas feed path 8 for the modified gas from modification part 2 is provided to transform portion 6.In addition, for the reformed gas from transform portion 6 is provided to purification part 10, be provided with reformed gas feed path 9.Purifying Purge gas (hydrogen) process hydrogen exhaust-duct 12 discharges that part 10 obtains.
In addition, supply with part 13 by first channel 13a by oxidant gas oxidant gas such as air are provided to modified gas feed path 8, provide oxidant gas to reformed gas feed path 9 through second passage 13b.
Then, in the apparatus for forming hydrogen of enforcement state 1 as the generation hydrogen of characteristic of the present invention the time the device working condition describe.
In the apparatus for forming hydrogen of the present invention, only the modification part 2 in upstream is provided with hot spots, and this hot spots work is heated modified catalyst 2a.Then, contact with modified catalyst 2a by raw material supplying passage 5 by raw material supplying part 1, carry out the water vapor modified-reaction through heating as fuel such as the hydro carbons of raw material and water.
As previously mentioned, be imported into transform portion 6 through modification gas (modified gas) partly through modified gas feed path 8, then, the reformed gas that obtains in transform portion 6 is imported into purification part 10 via reformed gas feed path 12.Then be discharged to the outside purifying the Purge gas (hydrogen) that part 10 obtains, for example fueling battery etc. by hydrogen exhaust-duct 9.
At this moment, in modified gas and reformed gas, be mixed into the air of supplying with part 13 from oxidant gas by first channel 13a and second passage 13b.Like this,, and hot spots is not set, the catalyst temperature of transform portion 6 and purification part 10 is risen, and can reach steady state in transform portion 6 and purification part 10 even only hot spots 4 is set in modification part 2.
In order to start apparatus for forming hydrogen at room temperature state, stablizing provides the less hydrogen of carbon monoxide content (Purge gas), and the temperature of the catalyzer of modification part 2, transform portion 6 and purification part 10 must be adapted to react requirement.Though apparatus for forming hydrogen of the present invention only is provided with hot spots in modification part 2, can effectively utilize the heat of modified gas and reformed gas, the catalyst temperature of each reactive moieties is tended towards stability.
That is, the feature of apparatus for forming hydrogen of the present invention is, not only can be to making the carbon monoxide oxidation concentration reduce, and import the reformed gas that purifies part and provide and be mixed into air, also can provide and be mixed into air to the modified gas that is imported into transform portion.
Below, the catalyst temperature of each reactive moieties of how stablizing the apparatus for forming hydrogen of the present invention that possesses above-mentioned formation is described in more detail.
Utilize 4 pairs of modification parts 2 of hot spots to heat, the temperature of modified catalyst body 2b is risen rapidly.The fuel that is modified by modified catalyst 2a changes modified gas into, then, changes reformed gas in transform portion 6, removes the carbon monoxide that comprises in the reformed gas and is cleaned purifying part 10.
Among the present invention, mixed the air of supplying with part from oxidant gas in the reformed gas before modified gas before importing transform portion 6 and the importing purification part 10.Like this, the airborne oxygen of supply and partially modified gas and reformed gas just can and purify in the part 10 in transform portion 6 respectively oxidizing reaction takes place, and produce the heat of oxidation.Utilize this heat just the catalyst temperature of transform portion 6 and purification part 10 to be heated to the temperature that is suitable for reacting rapidly.
The present invention so can control thermal value by the air capacity of supplying with, makes the control of catalyst temperature also become convenient owing to the heating that has utilized on conversion catalyst body 6a and the cleaning catalyst body 10a.
And, owing to making, the water vapor modified-reaction of fuel such as hydro carbons comprises a large amount of hydrogen in the modified gas, so, even transform portion and purify under the low-temperature condition of catalyzer after just starting of part oxidizing reaction is easily carried out.
In the enforcement state 1 of the present invention, because can heat respectively to each reactive moieties, to transform portion with purify the structure that part heats and compare, the structure that this heat of possessing by modified gas heats can make the catalyzer of each reactive moieties reach suitable temperature in the shorter time with successively.
In addition, the occasion that changes to some extent applicable to the flow of base feed (fuel and water) equally of this enforcement state.Base feed more after a little while because the absolute value of the heat possessed of modified gas reduces, so transform portion and the temperature that purifies part have the trend of reduction.Therefore, by the air capacity that the reduction adjustment corresponding to temperature provides, can generate heat and holding temperature in each reactive moieties.
Make the apparatus for forming hydrogen of aforementioned enforcement state 1 carry out real work.Running when at first, device being started describes.
Make hot spots 4 start the heating that begins modification part 2.Then, in 1 mole of methane gas (as the fuel hydro carbons of raw material), add the water more than 2 moles, in modification part 2, import modified catalyst 2a (by the platinum family precious metal prepare catalyzer).Utilize the heating heat of hot spots 4 that the modified catalyst temperature is controlled at about 700 ℃, make it carry out the water vapor modified-reaction.
Then, in the transform portion 6 of having filled the platinum family noble metal catalyst, import the modified gas of gained.Carbon monoxide content in the modified gas in the transform portion 6 reduces because of itself and water generation shift reaction.For making conversion catalyst body 6a promote the carrying out of shift reaction, need its temperature is risen to about 200～350 ℃ rapidly.Therefore, in modified gas, import air, utilize conversion catalyst body 6a to make partially modified gas generation oxidizing reaction, catalyzer is heated to the temperature that is suitable for reacting.The temperature decision that the air capacity of being supplied with is detected by conversion catalyst temperature measuring part, the ceiling temperature in the present embodiment is 350 ℃.
Then, make, and import purification part 10 in the reformed gas of transform portion 6 acquisitions and the air mixed of supply.In purifying part 10, utilize the oxygen oxidation to remove carbon monoxide.
Purifying part 10 also can be the same with transform portion 6, utilizes the cleaning catalyst body 10a with cleaning catalyst (platinum family oxide catalyst) to make part reformed gas component generation oxidizing reaction, catalyzer is heated to the temperature that is suitable for reacting.In the present embodiment, the air capacity that imports is controlled according to 100～200 ℃ the detected temperature of cleaning catalyst temperature measuring part.
In addition, the air capacity that imports transform portion 6 and purification part 10 must be set according to the amount of the hydrogen that is produced.As mentioned above, air being provided, the formation of each reactive moieties heating is compared with the formation that air is not provided in the present embodiment to transform portion 6 and purification part 10 in the present embodiment, the required time of temperature that the former reaches the catalyst temperature of each reactive moieties and is suitable for reacting is about the latter's 1/4.
Below, apparatus for forming hydrogen is in the standard state running describes.
The heating state of hot spots 4 is controlled so that the modified catalyst temperature reaches about 700 ℃, carried out the water vapor modified-reaction after stablizing.Under this standard state, the heat that utilizes modified gas to possess stops the supply of air with the flow of the temperature that can keep transform portion 6.
At this moment, be 100～200 ℃ even purify the temperature of part 10, by import to reformed gas carbon monoxide content be at least 1/2 contain the oxygen air, also can oxidation remove carbon monoxide.
In addition, the situation that the raw material supplying amount is changed to some extent also can adapt to rapidly.
If the raw material supplying amount improves 3 times, then do not provide air according to catalyst temperature, catalyst temperature will change a lot like this.When consequently, the carbon monoxide concentration that purifies part 10 exits is about normal operation 10 times.
On the other hand, according to catalyst temperature and during air supply, the carbon monoxide concentration in the time of keeping normal operation substantially.
In the present embodiment, the air feed rate is to be the catalyst temperature control of representative by detected temperatures that each catalyst temperature is measured part, if but the clear and definite operating condition of device also can set the air feed rate according to these conditions.
In addition, what use as oxygen-containing gas in the present embodiment is air, in fact so long as oxygen-containing gas all can use.In addition, what use as hot spots 4 is flame burner, as long as can heat modified catalyst in fact, can use any heating unit.
Below, the enforcement state 2 of apparatus for forming hydrogen of the present invention is described.
Fig. 2 is the simple longitudinal diagram that the apparatus for forming hydrogen of the invention process state 2 constitutes.Apparatus for forming hydrogen shown in Figure 2 has the formation identical with apparatus for forming hydrogen shown in Figure 1 basically, and working order is identical.Here, omit the explanation of both same sections, only difference is described.
Difference is to supply with part 13 at oxidant gas to be provided with the 3rd passage 13c, provides air by the raw material (fuel and water) of the 3rd passage before importing modification part 2.
During startup, be necessary equally that modified catalyst to modification part 2 heats to make its temperature reach the temperature that is suitable for reacting rapidly.Therefore, what this enforcement state adopted is to provide air to importing modification part 2 raw material before, makes the part material oxidation reach the formation of the purpose that modified catalyst is heated with modified catalyst.
Utilize above-mentioned formation that the catalyzer of each reactive moieties is heated to be suitable for separately the temperature of reacting, can further shorten the stable needed time of hydrogen that obtains.
In addition, because the absolute magnitude that provides air can reduce the hydrogen of acquisition to each reactive moieties, so the viewpoint that reduces from the air capacity that makes supply preferably takes fully to prevent the countermeasure of heat release to each reactive moieties and gas feed path.
Below, make the apparatus for forming hydrogen of aforementioned enforcement state 2 carry out work.
Raw material during except startup before importing modification part 2 provides air, makes outside this point of part material oxidation in modification part 2, and other running is all identical with previous embodiment 1.Compare with embodiment 1, the raw material before importing modification part 2 provides air, can make the catalyst temperature of modification part 2 reach design temperature quickly.
In the present embodiment, by in modification part 2, transform portion 6 with purify part 10 and use platinum group catalyst, can make carrying out because of being swift in response of air oxidation of fuel (hydro carbons) as raw material and modified gas.
Particularly unified the employing with platinum when being the formation of catalyzer of major constituent, it is easy that the recycle of the catalyzer when making catalyst recovery becomes.In addition, do not need catalyzer is reduced processing, and be difficult to cause the oxidation of catalyzer, so be easy to maintain because device shuts down the back entrained air.
Under the prerequisite that does not influence effect of the present invention, also can and purify the catalyzer that uses in the part 10 except that platinum group catalyst in modification part 2, transform portion 6.For example, use nickel catalyzator in modification part 2, use copper catalyst in transform portion 6, purifying part 10 use Au catalysts etc., those skilled in the art can make appropriate selection to being adapted to each catalyst for reaction.
In addition, the catalyst temperature of each reactive moieties can be set according to the catalyst system therefor kind.As the fuel of raw material, except methane,, comprise alcohols such as hydro carbons such as Sweet natural gas and LPG, methyl alcohol or petroleum naphtha etc. so long as water vapor modified feedstock commonly used gets final product.
According to enforcement state 1 of the present invention and 2, a part that makes oxygen in the air supply and raw material and modified gas is carried out oxidizing reaction by modification part, transform portion or the catalyzer that purifies part, produces the heat of oxidation.Utilize this heat the catalyzer of each reactive moieties promptly can be heated to the temperature that is suitable for reacting.In addition, because the heat of oxidation that modification, conversion and cleaning catalyst produce is used to heating, thus can control thermal value by the air capacity of supplying with, thus catalyst temperature can easily be controlled.
In addition, start to from device stably produce the hydrogen required time and shorten significantly in, the catalyst temperature of each reactive moieties when amount that produces hydrogen changes changes and also can adapt.
In addition, owing to do not need special heating unit in transform portion and purification part, so, can obtain fairly simple device and constitute.
Below, the enforcement state 3 of apparatus for forming hydrogen of the present invention is described.For the ease of understanding, describe successively with reference to the flow direction of accompanying drawing according to the fuel (unstripped gas) of apparatus for forming hydrogen of the present invention.
Fig. 3 is the structural simulation figure of an embodiment of apparatus for forming hydrogen of the present invention.
In the apparatus for forming hydrogen shown in Figure 3, fuel is 21 importings from the part of the fuel supply, and water vapor is supplied with part 22 by the fuel reforming water and imported.The unstripped gas of having mixed fuel and water vapor is heated by the passage with heat exchanging fin 23, generates modified gas with modified catalyst body 24 contact reactss that burner 25 heats then with through heating.At this moment, discharge combustion exhaust from venting port 26.Then, the CO content that utilizes CO conversion catalyst body 27 to reduce in the modified gas.Owing to will be used for polymer electrolyte fuel cell, so need CO concentration is reduced to the level of several ppm, therefore, purify the oxidant gas such as air of supplying with part 28 importing trace with oxidant gas by CO, utilize 29 oxidations of CO cleaning catalyst body to remove CO.The modified gas of having removed CO exports 30 fueling batteries etc. from modified gas.
As long as 21 fuel that import can produce hydrogen from the part of the fuel supply, it is not particularly limited.For example, can use various fuel such as hydro carbons such as Sweet natural gas, coal gas, liquefied petroleum gas (LPG), propane gas, kerosene, gasoline, methyl alcohol and dme, ethers and alcohols.In addition, the gas that also can use the petroleum gas that produces by the oil boom cracking and liquefied petroleum gas (LPG) to mix.Wherein, the major constituent of 13A gas is a methane, can use equally with Sweet natural gas.
Among the present invention, produced hydrogen,, can use the water vapor method of modifying that adds water vapor, also can use the adding air to carry out partially modified method, also can use the method for modifying of comprehensive above-mentioned two kinds of methods etc. as method of modifying by modification to aforementioned fuel.
Therefore,, can import water vapor, also can import the suitable air and the mixture of water vapor by water supply part 22 according to the kind of aforementioned method of modifying.
The ratio of the feed rate of fuel and water vapor is different because of fuel type, method of modifying kind, as long as change CO at fuel
2More than the stoichiometric ratio of hydrogen, and get final product in the scope that do not reduce of efficient.Specifically, stoichiometric ratio is 1～3.
When adopting water vapor modification method as method of modifying, the water vapor feed rate is in following scope.
Fuel type is 1 feed rate corresponding to fuel
Sweet natural gas 2～5
Kerosene 20～40
Gasoline 16～32
So-called " modification " generally be meant by fuel and water vapor or oxidant gas (for example oxygen) and produce hydrogen, and the hydrocarbon composition that utilizes the effect of heat or catalyzer to change fuel improves the operation of its proterties.Be meant among the present invention that fuel and water vapor and/or oxidant reactant gas generate hydrogen.
Contact with modified catalyst body 24 by the passage that possesses heat exchanging fin 23 with water vapor raw material (mixing) gas with the fuel that water supply part 22 imports by part of the fuel supply 21.Passage can by metals such as stainless steel (during low temperature also can with copper or aluminium etc.) etc. in the past material known constitute.Heat exchanging fin 23 also is a material known in the past.
The structure of modified catalyst body of the present invention has obvious characteristics.That is, for solve the problem of the pellet type catalyst body easy disintegrating that used in the past, present inventors are through conscientiously having invented the modified catalyst body with the following stated structure after the further investigation.
That is, modified catalyst body 24 is structures of supported catalyst component on the carrier with polynuclear plane, foam structure or ripple struction.
Adopt this structure can not cause the such disintegration of catalyzer in the past, can keep stable properties for a long time.And, compare with pellet type catalyst body in the past, owing to the contact area with unstripped gas increases considerably, can react effectively so have, when the catalyst system therefor amount is reduced, the advantage that the thermal capacity of catalyst body also can be less.
In addition, because the surface-area of unit volume is bigger, so because of the heat release of radiation and convection current also increases, thereby also have the advantage that heat conductivity increases.And the heat that burner for heating 5 is produced can pass to whole modified catalyst body equably, so, can remove reaction heat rapidly.
Below, the preparation method of modified catalyst body 24 is described.
After the powder of modified catalyst (catalyst component) and dispersion medium be mixed and made into slurry, on carrier, make its drying just make modified catalyst body 24 this slurry coating (coating).
As modified catalyst,, be not particularly limited as long as have the effect that can promote by fuel and water vapor and/or oxygen generation hydrogen.For example, nickel class catalyzer such as carrying alumina nickel, noble metal catalysts such as carrying alumina ruthenium and carrying alumina rhodium etc.
Among the present invention, it is Powdered to utilize ordinary method that modified catalyst is ground into.The particle diameter of powder does not need only in the time of can not influencing dispersiveness and be carried on carrier when the preparation slurry and can not peel off, and it is not particularly limited, and specifically is advisable with 0.1～2 μ m.
Make modified catalyst powder dispersive dispersion medium as long as disperse easily after the gained slurry coated carrier, it also is not particularly limited.Specifically can make water and alcohols etc.
The used carrier of the present invention has polynuclear plane, foam structure or ripple struction.As previously mentioned, so just can increase contact area with unstripped gas.When having the foam structure, if each bubble all is independently, then unstripped gas is difficult for passing through, so preferably each bubble all is the structure that is communicated with.
As solid support material,, it is not particularly limited as long as in the bigger atmosphere gas of hydrogen content He under the hot conditions, can stablize.For example, can use heat-resistant inorganic materials such as trichroite, aluminum oxide, sial, mullite, the contour thermally-conductive materials of silicon carbide, various stainless steel and other metal materials etc.
When aforementioned heat-resistant inorganic material uses for a long time, has the advantage of the performance that can keep stable under hot conditions.
Aforementioned high thermal conductivity material has the temperature distribution homogenization that can make gained modified catalyst body 24, temperature control is become easily, and can improve the advantage of reaction efficiency.
In addition, when using the aforementioned metal material, has the advantage of easy-formation and high vibration resistance.
Utilize previous materials, by extrusion molding, soldering etc. in the past known method can make above-mentioned carrier.
Can adopt the known method that paint field was general in the past to carry out to the coating of aforementioned bearer, for example, spraying method and roller painting etc.
As for drying, but but also heat drying of seasoning.If but the too high function that may destroy catalyzer of Heating temperature, so this point should be noted that.
The modified catalyst component is to different and different according to the kind of catalyst component and the kind of fuel gas etc. of the glue spread of carrier, and those skilled in the art can make appropriate selection.
The logical out of date Heating temperature based on fuel kind of unstripped gas of the modified catalyst body 24 that obtains according to preceding method and modified catalyst kind etc. different and different, briefly, as long as this temperature can make fuel carry out modified-reaction generation hydrogen.
Below, enumerated the Heating temperature scope of different fuel.
Fuel type Heating temperature scope (℃)
Sweet natural gas (gas) 500～800
Propane gas 500～800
Kerosene 500～800
Gasoline 500～800
Methyl alcohol, dme 200～400
Generally except hydrogen, also comprise CO (for example, be fuel, comprise about 10% CO when under 500～800 ℃ temperature, carrying out modification) in the modified gas that unstripped gas forms by modified catalyst body 24 with the Sweet natural gas.On the other hand, when the hydrogen that utilizes apparatus for forming hydrogen of the present invention to obtain is used for as polymer electrolyte fuel cell, CO concentration need be reduced to the level about thousands of ppm～1%.Therefore, make above-mentioned modified gas the CO concentration in the modified gas is reduced to level about thousands of ppm～1% by CO conversion catalyst body 27.
The preparation method of CO conversion catalyst body 27 is except catalyst system therefor kind difference, and all the preparation method with aforementioned modified catalyst body 24 is identical for other.
As long as used here CO conversion catalyst body has the CO of making and steam reaction generates CO
2Get final product with the function of hydrogen, it is not particularly limited.For example, generally use Cu-Zn series catalysts, Fe-Cr series catalysts etc.That is, " CO conversion " here is to instigate CO and steam reaction, produces CO
2And hydrogen, make CO concentration be reduced to lower concentration (as below 1～2%) by high density (as 10%).
When acting as a fuel use with methyl alcohol and dme etc., can under lower Heating temperature, carry out modification, because the CO concentration that comprises in the modified gas is also lower,, CO cleaning catalyst body 29 described later can only be set also sometimes so can omit CO conversion catalyst body 27.
When hydrogen is used for polymer electrolyte fuel cell, preferably CO concentration is reduced to the level of several ppm.Therefore, in the apparatus for forming hydrogen of the present invention, the modified gas of process CO conversion catalyst body 27 imports CO cleaning catalyst body 29 by passage c, and the minute quantity CO that comprises is removed in oxidation.At this moment, owing to making the CO oxidation need oxygen, so, be provided with purification the passage from conversion catalyst body 27 to cleaning catalyst body 29 and supply with part 28 with oxidant gas, the modified gas through CO conversion catalyst body 27 is contacted with CO conversion catalyst body 27 with air.
The preparation method of CO cleaning catalyst body 29 is except catalyst system therefor kind difference, and other are all identical with preparation aforementioned modified catalyst body 24.Oxidation package is contained in the function of the CO in the modified gas as long as used here CO cleaning catalyst has optionally, or the methanation function that makes CO change hydrogen into gets final product, and it is not had special the qualification.For example, the Pt series catalysts of alumina load and Ru series catalysts etc.In addition, when in the fuel cell that the CO that contains hundreds of～thousands of ppm can also work, using the hydrogen that apparatus for forming hydrogen of the present invention makes, can omit CO cleaning catalyst body 29.To take out from modified gas outlet 30 through the modified gas of above-mentioned CO cleaning catalyst body 29, for example can be used for fuel cell etc.
In the apparatus for forming hydrogen of the present invention, the most handy thermal insulation material covers the outside of container that each catalyst body is housed and passage etc.
In addition, because it is different with heat transfer condition that the most desirable temperature of modified catalyst body 24, CO conversion catalyst body 27 and CO cleaning catalyst body 29 distributes, so, the carrier of heat conductivity good metal system polynuclear plane can be used in the modified catalyst body 24, the carrier of trichroite system polynuclear plane can be used in CO conversion catalyst body 27 and the CO cleaning catalyst body 29.In a word, can from heat-resistant inorganic material, metallic substance and high thermal conductivity inorganic materials, make various effective choice.
When using the carrier of polynuclear plane, be included in its central position metal bar is set, grade with different material formation upstream portion and downstream portion, or in same catalyst body, carry out compoundization for improving effective means that temperature distribution adopts.
If carry out the water vapor of partially modified method replacement from water supply part 22 with the adding air, though the hydrogen amount that is included in the modified gas reduces than regular meeting, but in modified catalyst body 24, carry out to cause combustion reactions in the modification, make the heating of catalyst body become easy.In this case, have the carrier of polynuclear plane, can increase the contact area of unstripped gas and modified catalyst body, thereby react effectively by use.
When importing air and water vapor simultaneously, can obtain characteristic between water vapor modification and partially modified.
Utilize as materials such as stainless steels, take ordinary method can make the container of inner each catalyst body of containing and passage etc.
Below, the present invention will be described by embodiment, but the present invention is not limited to this.
The separated pulverizing modification with, CO transform with and the CO purification with pellet type catalyst body (particle diameter is about 1 μ m), according to catalyst component: the ratio of water=1: 2 (weight) is dispersed in the water it, makes slurry.Above-mentioned slurry is coated on the carrier with polynuclear plane of trichroite system, has just made modified catalyst body 24, CO conversion catalyst body 27 and CO catalyst for clarifying body 29.
Above-mentioned catalyst body is installed in the apparatus for forming hydrogen shown in Figure 3.Import the gas of handling through desulfurization with 50 liters/minute speed by part of the fuel supply 21, import water vapors with 150 liters/minute speed by water supply part 22, utilize heating the temperature heating of modified catalyst body 24 to be risen to about 800 ℃ and make to react and carry out then with burner 25.
To remove by the water vapor in the generation gaseous fraction behind the modified catalyst body 24, measure, record that hydrogen is about 80%, CO is about 12%, carbonic acid gas is about 8%, methane is about 500ppm with vapor-phase chromatography.
Modified gas changes about 3000ppm into by CO conversion catalyst body 27 back CO concentration, supplies with part 28 importing air by oxidant gas again this moment and makes oxygen concn reach 2%, utilizes CO cleaning catalyst body 29 reaction back CO concentration to reduce to 5ppm.
Apparatus for forming hydrogen is temporarily quit work, and then start, after such operation carried out 1500 times repeatedly modified gas formed and measure, record by the methane concentration behind the modified catalyst body 24 and be 800ppm, be about 4500ppm, reduce to 7ppm by the CO concentration behind the CO cleaning catalyst body 29 by the CO concentration behind the CO conversion catalyst body 27.
Embodiment 4
Apparatus for forming hydrogen, fuel cell and the CD-ROM drive motor that embodiment 3 is made packed in the car together, carries out the test of 100,000 kilometers operations.
Behind the end of run, the same with embodiment 3, with the composition of gas chromatography determination modified gas, record by the methane concentration behind the modified catalyst body 24 and be 1000ppm, be about 4800ppm, be 9ppm by the CO concentration behind the CO cleaning catalyst body 29 by the CO concentration behind the CO conversion catalyst body 27.
Except being that stainless steel replaces the material of trichroite as the carrier with polynuclear plane with Fe-Cr-Al, all the other are all identical with embodiment 3, make apparatus for forming hydrogen work.
With the generation gas composition that gas chromatography determination is removed water vapor after by modified catalyst body 24, record that hydrogen is about 80%, CO is about 12%, carbonic acid gas is about 8%, methane is about 300ppm.
Be about 2500ppm by the CO concentration behind the CO conversion catalyst body 27, supply with part 28 importing air by oxidant gas then and make oxygen concn reach 2%, reduce to 3ppm in CO cleaning catalyst body 29 reaction back CO concentration.
Apparatus for forming hydrogen is temporarily quit work, and then start, after such operation carried out 1500 times repeatedly modified gas formed and measure, record by the methane concentration behind the modified catalyst body 24 and be 700ppm, be about 4000ppm, reduce to 6ppm by the CO concentration behind the CO cleaning catalyst body 29 by the CO concentration behind the CO conversion catalyst body 27.
Comparative example 1
As shown in Figure 4, the modification of not pulverizing embodiment 3 uses is used, CO transforms and uses, CO purifies and uses the pellet type catalyst body, they are packed into separately in the container, import the gas of handling through desulfurization with 50 liters/minute speed by part of the fuel supply 31, import water vapor by water supply part 32 with 150 liters/minute speed.
Similarly to Example 3, with burner heat modification catalyst body 34 reaction is carried out with heating, with the generation gas composition that gas chromatography determination is removed water vapor after by modified catalyst body 34, record that hydrogen is about 80%, CO is about 12%, carbonic acid gas is about 8%, methane is 600ppm.
The CO concentration of modified gas after by CO conversion catalyst body 37 is about 3500ppm, supplies with part 38 by oxidant gas then and imports air and make oxygen concn reach 2%, reduces to 6ppm in CO cleaning catalyst body 39 reaction back CO concentration.
Apparatus for forming hydrogen is temporarily quit work, and then start, after such operation carried out 1500 times repeatedly modified gas formed and measure, recording by the methane concentration behind the modified catalyst body 34 and be 9000ppm, be about 14500ppm by the CO concentration behind the CO conversion catalyst body 37, is 5500ppm by the CO concentration behind the CO cleaning catalyst body 39.If catalyst body is taken out from reaction chamber, can find that disintegration has taken place the part catalyst body, size becomes about 3/4 of the initial stage.
Comparative example 2
Apparatus for forming hydrogen, fuel cell and the CD-ROM drive motor of comparative example 1 are packed in the car together, similarly to Example 4, carry out 100,000 kilometers test run(s)s.
Behind the end of run, with the composition of gas chromatography determination modified gas, record by the methane concentration behind the modified catalyst body 34 and be 20000ppm, be about 16000ppm, be about 9000ppm by the CO concentration behind the CO cleaning catalyst body 39 by the CO concentration behind the CO conversion catalyst body 37.
If the pellet type catalyst body is taken out from reaction chamber, can find that serious disintegration takes place catalyst body, size becomes about 1/2 of the initial stage.
Compare and obviously to find out by assessment result the device of the foregoing description and comparative example, enforcement state 3 of the present invention provides catalyzer is prolonged work-ing life, can suppress to restart the influence that is caused with high vibration, the apparatus for forming hydrogen that can work steadily in the long term because of device shuts down repeatedly.
Enforcement state 4
Below, with reference to the accompanying drawings enforcement state 4 of the present invention is described.
Fig. 5 is the simple pie graph of the enforcement state 4 of apparatus for forming hydrogen of the present invention.
In the apparatus for forming hydrogen shown in Figure 5, fuel is 41 importings from the part of the fuel supply, and water vapor is supplied with part 42 by the fuel reforming water and imported.The unstripped gas that fuel and water vapor mix is heated by the passage with heat exchanging fin 43, generates modified gas with modified catalyst body 46 contact reactss of burner 44 heating then with through heating.At this moment, discharge combustion exhaust from venting port 45.Then, the CO content that utilizes CO conversion catalyst body 47 to reduce in the modified gas.Owing to will be used for polymer electrolyte fuel cell, so need CO concentration is reduced to the level of several ppm, therefore, purify the air of supplying with part 48 importing trace with oxidant gas by CO, utilize 49 oxidations of CO cleaning catalyst body to remove CO.The modified gas of having removed CO uses as fuel cell from modified gas outlet 50 supplies.
Be provided with first strainer 51 and second strainer 52 in the downstream side of modified catalyst body 46 and CO conversion catalyst body 47 respectively.
For reactor is remained on certain temperature, the each several part of also available thermal insulation material cladding system.Can adopt in the past the material that uses as catalyst body, preferably with the Ni catalyzer as the modified catalyst body, the Cu-Zn catalyzer is as CO conversion catalyst body, the Pt catalyzer is as CO cleaning catalyst body.
The fuel that produces modified gas comprises gas (Sweet natural gas), propane, kerosene, gasoline, methyl alcohol and dme etc.Used method of modifying comprises the water vapor modification method that imports water vapor, import the partially modified method of air and make up the method for modifying etc. of above-mentioned two kinds of reactions.
Here, be that the example that fuel carries out the water vapor modification is that representative is illustrated with the Sweet natural gas.But, also can use other fuel, adopt partially modified and made up the partially modified and method of modifying water vapor modification, though the composition of the modified gas that generates more or less changes, and the temperature condition during modification is different, present method is all applicable.
Below, the running characteristic of the apparatus for forming hydrogen of the present invention of enforcement state 4 is described.
Import fuel by part of the fuel supply 41, import the water vapor that is equivalent to 3 times of amounts of fuel by water supply part 42.Mixed unstripped gas, and is heated to modified catalyst body 46 about 500～800 ℃ and contacts and react the generation modified gas with burner 44 heating through heating.Because except hydrogen, also comprise the CO about 10% in the modified gas, so, utilize CO conversion catalyst body 47 that carbon monoxide concentration is reduced to about thousands of ppm～1%.If gained hydrogen will be used for polymer electrolyte fuel cell, then CO concentration must be reduced to the level of several ppm, therefore, supply with the air that part 48 imports trace by oxidant gas, utilize 49 oxidations of CO cleaning catalyst body to remove CO.The modified gas of having removed CO exports 50 fueling batteries by modified gas and uses.
As previously mentioned, when being used for automobile and housekeeping fuel cell system, need to start repeatedly continually and stop, can bring violent thermal shocking to each catalyst body in this case.During especially for automobile, operating vibration is more strong.If device is running for a long time under these conditions, then catalyzer is known from experience slowly disintegration and is broken and micronization.At this moment, though the reactivity of catalyst body itself is not had too big influence, the catalyst fines that comes off from catalyst body can disperse to the downstream side.When phenomenon that this catalyst fines disperses occurring, powder mainly is positioned at the catalyst body in the downstream side of the catalyst body that disperses and catches.Specifically, modified catalyst is caught by the CO transform portion, and the CO conversion catalyst is purified part by CO and catches.
Usually, under the temperature condition that the CO conversion catalyst is worked, can be used as the methanation catalyst use owing to be suitable as the catalyzer of the modified catalyst of hydro carbons, so the catalyst fines that disperses out from the modified catalyst body has finally caused the reduction of methane conversion.And, if the powder that is dispersed out by CO conversion catalyst body is caught by CO cleaning catalyst body, can cause detrimentally affect equally.Purify in the part at CO, make CO carry out optionally oxidation though import air, but the selectivity of CO oxidation is reduced by the CO conversion catalyst that CO cleaning catalyst body is caught, and near the CO conversion catalyst that arrives the CO cleaning catalyst downstream part reacts carbonic acid gas and hydrogen because of the countertransference reaction, thereby causes the rising of CO concentration.
On the other hand, as described in this enforcement state 4, respectively when modified catalyst body and CO conversion catalyst body downstream side are provided with first strainer 51 and second strainer 52, the above-mentioned catalyst fines that disperses is not caught by CO conversion catalyst body and CO cleaning catalyst body, and device can be worked steadily in the long term.
In this case, the temperature of first strainer 51 of modified catalyst body 46 downstream parts is not preferably carried out the temperature of methanation reaction in fact.Because the methane modified-reaction is the balanced reaction that depends on temperature, can carry out methanation reaction in the temperature range about 300～400 ℃, therefore, the methane turnover ratio decreases.In this enforcement state, preferably by making first strainer 51 make the temperature of its temperature near modified catalyst body 46 near the downstream part of modified catalyst body 46.In addition, the temperature that methanation reaction is carried out is meant the methane turnover ratio according to destination apparatus in fact, and methane concentration generally is no more than 1～5% temperature range.
The strainer that first strainer 51 and second strainer 52 can use the fiber be made up of metal, pottery or their complex body to constitute.In addition, mesh-shape, the cellular or foam shape strainer that also can use metal, pottery or their complex body to form.
The making method of strainer comprises that the fiber that thermotolerance materials such as stainless steel, glass, quartz are formed is arranged on the inner method of pipe with the standard of counting cm thick, or in advance with the method for fiber compressed moulding for the number mm thick.
Above-mentioned strainer is the device that can capture the catalyst fines that disperses, and it is stable fully that its material can keep under working conditions.In addition because its surface is porous, so the catalyzer that disperses by the time more than half being hunted down arranged.
In this enforcement state, first strainer 51 and second strainer, 52 operated by rotary motion in order to increase filtration area, can enlarge the passage of strainer part in more small-bore passage, or make the shape bending of strainer, so just can suppress the increase of the pressure-losses of the strainer that causes because of obstruction.
The pressure-losses that causes owing to the obstruction of strainer is bigger, so be preferably in the upstream side and the downstream side of first strainer 51, second strainer 52 pressure detector is set.If it is big that the pressure-losses of strainer becomes, then the load of the pump of transfer the fuel etc. just increases, and causes efficient to reduce.Therefore, by the pressure before and after the strainer is detected, just can obtain the pressure-losses that first strainer 51 and second strainer 52 cause.If in time change strainer when reaching predefined standard value, apparatus for forming hydrogen just can be worked long-term and stably.
Because what use in this enforcement state is polymer electrolyte fuel cell, CO concentration need be reduced to the level of several ppm, so, the device that all is provided with modified catalyst body, CO conversion catalyst body and CO cleaning catalyst body is illustrated.If it is that the modified gas of hundreds of～thousands of ppm also can be worked that fuel cell utilizes CO concentration, then need not to be provided with CO cleaning catalyst body.
In addition, when using methyl alcohol and dme, under the low temperature about 300 ℃, just can carry out modification as fuel, because the CO concentration after the modification is lower, so, even CO conversion catalyst body is not set, only depend on CO cleaning catalyst body also can work sometimes.In this case, owing to used as this class of copper-zinc system catalyst and the similar catalyzer of CO conversion catalyst as modified catalyst, so, exist CO conversion catalyst with present embodiment to disperse influence that the same catalyst fines that disperses causes, the downstream side that therefore is preferably in the modified catalyst body is provided with strainer.
In this enforcement state, example to the water vapor modification of fuel is narrated, when carrying out partially modified replacement water vapor modification with the importing air, hydrogen amount contained in the modified gas reduces than regular meeting, but on catalyst body, carry out in the modification combustion reactions taking place, become easy with regard to the heating that makes catalyst body like this.In addition, when importing air and water vapor simultaneously, can obtain characteristic between water vapor modification and partially modified.
The modified catalyst body preferably uses Ni series catalysts component, and CO conversion catalyst body preferably uses Cu-Zn series catalysts component, and CO cleaning catalyst body preferably uses Pt series catalysts component.As long as the catalyzer among the present invention has activity can promote modified-reaction, CO conversion reaction and CO to purify reaction respectively, it is not particularly limited.
The shape of catalyst body can be a particulate state, also can use honeycombed catalyst body etc., and the catalyst body of other shapes also can use certainly.
Anti-sputtering device used in the present embodiment is a strainer, but so long as can prevent that the device that disperses of catalyst fines from just can utilize modified gas stream in the passage of catalyst body downstream side to blow afloat powder and making its accumulation and capture, or the pipe inside of passage is carried out surface treatment and made powder absorption etc.
Fig. 6 is the simple pie graph of this enforcement state.First strainer 71 is arranged on the position intermediate near modified catalyst 66 and CO conversion catalyst body 67, and temperature is also in both centres, in 400～500 ℃ scope.If caught by first strainer 71 by the catalyzer that modified catalyst body 66 disperses, it is temperature required and generate heat then to reach methanation reaction.This thermal value is directly proportional with the catalytic amount that disperses of being caught by first strainer 71, by measuring temperature with nigh thermopair 73 is set, just can estimate the catalytic amount that disperses that first strainer 71 is caught.When the temperature of first strainer 71 reaches predefined standard value, apparatus for forming hydrogen is worked steadily in the long term if in time change strainer.
In this enforcement state, as shown in Figure 6, make thermopair neighbor filter downstream side, outside according to its also contiguous upstream side of structure, side or the pipe of device.In addition, temperature-detecting device can send the detection means of signal after can use thermistor and bimetal etc. that temperature is detected.
Below, utilize embodiment that enforcement state 4 and 5 of the present invention is described in more detail, but the present invention is not limited to this.
Filling is packed into and is the modified catalyst body 46 formed of modified catalyst, is the conversion catalyst body 47 that the CO conversion catalyst is formed by Cu-Zn by Ni respectively in apparatus for forming hydrogen shown in Figure 5, and is the cleaning catalyst body 49 that CO selective oxidation catalyzer is formed by Pt.The line of being made by stainless steel directly is the downstream side that first strainer 51 that constitutes of the steel fiber of 0.1 μ m and second strainer 52 are separately positioned on modified catalyst body 46 and CO conversion catalyst body 47.The gas of handling through desulfurization 41 imports from the part of the fuel supply with 50 liters/minute speed, and water vapor is imported by water supply part 42 with 150 liters/minute speed.Utilizing heating to make the temperature of modified catalyst body 46 rise to about 800 ℃ with burner 44 heating reacts.
Form by the modified gas behind the modified catalyst body 46 with gas chromatography determination and to find, remove water vapor, hydrogen concentration is about 80%, CO concentration is about 11%, gas concentration lwevel is about 9%, methane concentration is about 0.05%.Again, forming by the modified gas behind the CO conversion catalyst body 47 is that methane and CO concentration are respectively 0.05% and 0.3%.By CO cleaning catalyst body 49 back CO concentration is 8ppm.In addition, first strainer 51 that records and the temperature of second strainer 52 are respectively 700 ℃ and 150 ℃.
Make the apparatus for forming hydrogen break-off, restart, carry out 1500 such operations repeatedly, measure the composition of modified gas equally.By the methane concentration in the gas of first strainer, 51 front and back and by the methane concentration in the gas behind the CO conversion catalyst body 47 all for O.06%.By the CO concentration in the gas behind the CO cleaning catalyst body 49 is 9ppm.Measure the pressure of first strainer 51 and second strainer, 52 front and back, the pressure-losses of initial stage pressure is respectively 20mAq and 40mAq.Strainer is taken out from device, measure the weight of catalyst fines attached thereto, find that the weight of first strainer 51 and second strainer 52 increases 12g and 38g respectively.
Apparatus for forming hydrogen, fuel cell and CD-ROM drive motor linked together pack in the car, carry out the test of 20,000 kilometers operations.After the operation, with vapor-phase chromatography modified gas being formed similarly to Example 5 and measured, all is 0.08% by the methane concentration in the gas of first strainer, 51 front and back with by the methane concentration in the gas behind the CO conversion catalyst body 47.By the CO concentration in the gas behind the CO cleaning catalyst body 49 is 10ppm.
Embodiment 8
As shown in Figure 6, first strainer 71 is arranged on the mid-way of modified catalyst body 66 and CO conversion catalyst body 67.Thermopair 73 is set it is contacted with first strainer 71, utilize tester to read the signal of thermopair 73.
Import the gas of handling through desulfurization with 50 liters/minute speed by part of the fuel supply 61, import water vapor with 150 liters/minute speed by water supply part 62 they are reacted.Be that hydrogen is about 80%, CO is about 11%, carbonic acid gas is about 9%, methane about 0.05% by the gas composition behind the modified catalyst body 66.By the gas composition behind the CO conversion catalyst body 67 is that methane and CO are respectively 0.05% and 0.3%.By the CO concentration behind the CO cleaning catalyst body 69 is 8ppm.
Similarly to Example 5, make the apparatus for forming hydrogen break-off, then start, after stopping repeatedly starting 1500 times, measure modified gas and form.By the methane concentration in the gas behind the modified catalyst body 66 is 0.06%, is 5.5% by the methane concentration in the gas behind the CO conversion catalyst body 27.By the CO concentration in the gas behind the CO conversion catalyst body 27 is 0.3%, is 10ppm by the CO concentration in the gas behind the CO cleaning catalyst body 29.In addition, the temperature of first strainer 71 has risen 15 ℃ than the initial stage.First strainer 71 is taken out from device, find after measuring catalyst fines weight attached thereto, adhered to the 12g catalyst fines on first strainer 71.
Then, replace aforementioned first strainer 71, start once more behind the apparatus for forming hydrogen of packing into new strainer.Consequently, all be 0.06% by the methane concentration in the gas of first strainer, 71 front and back with by the methane concentration in the gas behind the CO conversion catalyst body 27.In addition, be 9ppm by the CO concentration in the gas behind the CO cleaning catalyst body 29.
Comparative example 3
As different from Example 5, remove first strainer 51 and second strainer 52 reacts gas and water.Import the gas of handling through desulfurization with 50 liters/minute speed by part of the fuel supply 41, import water vapor with 150 liters/minute speed by water supply part 42 they are reacted.The composition of modified gas is, hydrogen is about 80%, CO is about 11%, carbonic acid gas is about 9%, methane is about 0.05%.Forming by the modified gas behind the CO conversion catalyst body 27 is that methane and CO are respectively 0.05% and 0.3%.By the CO concentration in the gas behind the CO cleaning catalyst body 29 is 8ppm.
Similarly to Example 5, make the apparatus for forming hydrogen break-off, restart, carry out 1500 aforesaid operations repeatedly after, measure modified gas and form.By the methane concentration in the gas behind the modified catalyst body 24 is 0.06%, is 5.5% by the methane concentration in the gas behind the CO conversion catalyst body 27.By the CO concentration in the gas behind the CO conversion catalyst body 27 is 0.3%, is 350ppm by the CO concentration in the gas behind the CO cleaning catalyst body 29.
The assessment result of the device of above embodiment 6～8 and comparative example 3 can obviously be found out, the invention process state 4 and 5 apparatus for forming hydrogen can prevent to shut down repeatedly and start because of device, or high vibration and the catalyzer that causes disperses phenomenon, thereby make device steady running for a long time.
Claims (12)
1. apparatus for forming hydrogen, described device possesses that part is supplied with in part of the fuel supply, fuel reforming water, oxidant gas is supplied with part, modified catalyst body, aforementioned modified catalyst usefulness hot spots, CO conversion catalyst body and CO cleaning catalyst body, and begins to dispose successively along the downstream side modified catalyst body, CO conversion catalyst body and CO cleaning catalyst body from aforementioned part of the fuel supply; The feature of described device is, partly import fuel and water to aforementioned modification through heating, at the aforementioned modified gas that is imported into aforementioned transform portion and in the aforementioned reformed gas that purifies part of being imported into of obtaining of aforementioned transform portion, be mixed into aforementioned oxidant gas and supply with the oxidant gas that part provides, make aforementioned modified gas in aforementioned transform portion and the aforementioned purification part and at least a portion in the aforementioned reformed gas that oxidation take place respectively.
2. apparatus for forming hydrogen as claimed in claim 1 wherein, comprises platinum group catalyst at least in the conversion catalyst of aforementioned conversion catalyst body.
3. apparatus for forming hydrogen as claimed in claim 1 or 2 wherein, has the conversion catalyst temperature measuring part of measuring aforementioned conversion catalyst body temperature degree, by the oxidant gas amount that adjusting is mixed in the aforementioned modified gas conversion catalyst temperature is controlled.
4. as each described apparatus for forming hydrogen of claim 1～3, wherein, have the cleaning catalyst temperature measuring part of measuring aforementioned cleaning catalyst body temperature degree, the cleaning catalyst temperature is controlled by the oxidant gas amount that adjusting is mixed in the aforementioned reformed gas.
5. as each described apparatus for forming hydrogen of claim 1～4, wherein, make from being mixed into aforementioned oxidant gas in the fuel of aforementioned part of the fuel supply and water supply part and the water and supply with the oxidant gas that part provides.
6. apparatus for forming hydrogen as claimed in claim 5 wherein, has the modified catalyst temperature measuring part of measuring aforementioned modified catalyst body temperature degree, by the oxidant gas amount that adjusting is mixed in aforementioned fuel and the water modified catalyst temperature is controlled.
7. as each described apparatus for forming hydrogen of claim 1～6, wherein, modified catalyst body, CO conversion catalyst body and CO cleaning catalyst body are selected from the carrier with polynuclear plane, foam structure or ripple struction that is loaded with catalyst component.
8. as each described apparatus for forming hydrogen of claim 1～7, wherein, aforementioned fuel reforming water is supplied with part air also is provided when water vapor is provided.
9. as each described apparatus for forming hydrogen of claim 1～8, wherein, aforementioned fuel reforming water is supplied with part air only is provided.
10. as each described apparatus for forming hydrogen of claim 1～9, wherein, between aforementioned modified catalyst body and aforementioned CO conversion catalyst body, and at least one place between aforementioned CO conversion catalyst body and the CO cleaning catalyst body is provided with anti-sputtering device.
11. apparatus for forming hydrogen as claimed in claim 10, wherein, aforementioned anti-sputtering device is a strainer, and the pressure-detecting device that is used to detect the pressure-losses of aforementioned strainer is set at the upstream side and the downstream side of aforementioned strainer.
12. apparatus for forming hydrogen as claimed in claim 11 wherein, is provided with temperature-detecting device in the position of contiguous aforementioned strainer.
Applications Claiming Priority (6)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6895599A JP2000264603A (en) | 1999-03-15 | 1999-03-15 | Hydrogen generator |
| JP068955/1999 | 1999-03-15 | ||
| JP081076/1999 | 1999-03-25 | ||
| JP8107699A JP2000272902A (en) | 1999-03-25 | 1999-03-25 | Hydrogen generation apparatus |
| JP112787/1999 | 1999-04-20 | ||
| JP11278799A JP2000302409A (en) | 1999-04-20 | 1999-04-20 | Apparatus for generating hydrogen |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1266814A true CN1266814A (en) | 2000-09-20 |
| CN1189386C CN1189386C (en) | 2005-02-16 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN00104316.1A Expired - Fee Related CN1189386C (en) | 1999-03-15 | 2000-03-15 | Hydrogen producer |
Country Status (4)
| Country | Link |
|---|---|
| US (1) | US6733552B1 (en) |
| EP (1) | EP1036757B1 (en) |
| CN (1) | CN1189386C (en) |
| DE (1) | DE60010555T2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100393608C (en) * | 2002-08-20 | 2008-06-11 | 千年电池公司 | System for hydrogen generation |
| CN107098310A (en) * | 2016-02-23 | 2017-08-29 | 苏州芷宁信息科技有限公司 | A kind of continuous hydrogen-feeding system |
Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE10065473A1 (en) * | 2000-12-28 | 2002-07-04 | Basf Ag | Process and converter for the catalytic conversion of fuel |
| US7147680B2 (en) * | 2001-01-26 | 2006-12-12 | Matsushita Electric Industrial Co., Ltd. | Hydrogen purification apparatus and method and fuel cell power generation system and method |
| JP3870783B2 (en) * | 2001-12-27 | 2007-01-24 | 日産自動車株式会社 | Exhaust gas purification system for fuel cell vehicle and purification method for exhaust gas of fuel cell vehicle |
| US7118717B2 (en) | 2002-09-06 | 2006-10-10 | Engelhard Corporation | Simplified article for carbon monoxide removal |
| US6932848B2 (en) * | 2003-03-28 | 2005-08-23 | Utc Fuel Cells, Llc | High performance fuel processing system for fuel cell power plant |
| US20050106427A1 (en) * | 2003-11-17 | 2005-05-19 | Ford Motor Company | Direct operation of low temperature solid oxide fuel cells using oxygenated fuel |
| US7967820B2 (en) * | 2006-02-07 | 2011-06-28 | P Tech, Llc. | Methods and devices for trauma welding |
| US20080016768A1 (en) | 2006-07-18 | 2008-01-24 | Togna Keith A | Chemically-modified mixed fuels, methods of production and used thereof |
| US8697451B2 (en) * | 2010-11-22 | 2014-04-15 | Fuelcell Energy, Inc. | Sulfur breakthrough detection assembly for use in a fuel utilization system and sulfur breakthrough detection method |
| US9070915B2 (en) * | 2011-10-20 | 2015-06-30 | Panasonic Intellectual Property Management Co., Ltd. | Hydrogen generator, operating method of hydrogen generator, and fuel cell system |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3919114A (en) * | 1969-11-21 | 1975-11-11 | Texaco Development Corp | Synthesis gas process |
| US3666682A (en) * | 1969-11-26 | 1972-05-30 | Texaco Inc | Water-gas shift conversion process |
| US3900646A (en) * | 1973-02-21 | 1975-08-19 | Robert A Clyde | Method of plating metal uniformly on and throughout porous structures |
| US4863707A (en) * | 1982-09-30 | 1989-09-05 | Engelhard Corporation | Method of ammonia production |
| JP2835182B2 (en) | 1990-01-18 | 1998-12-14 | 株式会社東芝 | Catalytic reactor used for gas phase reaction |
| JPH10101302A (en) | 1996-09-24 | 1998-04-21 | Toyota Motor Corp | Device for reducing carbon monoxide concentration and method for reducing carbon monoxide concentration |
| JP3870455B2 (en) | 1996-09-27 | 2007-01-17 | トヨタ自動車株式会社 | Carbon monoxide concentration reducing device and method, and fuel cell power generator |
| JP3843509B2 (en) | 1996-11-08 | 2006-11-08 | 石川島播磨重工業株式会社 | Plate reactor |
| DE19727588C1 (en) | 1997-06-28 | 1999-02-18 | Dbb Fuel Cell Engines Gmbh | Device for generating a hydrogen-rich and low-carbon monoxide gas |
| US6562088B2 (en) * | 1998-09-09 | 2003-05-13 | Matsushita Electric Industrial Co., Ltd. | Method for operating a hydrogen generating apparatus |
-
2000
- 2000-03-13 DE DE60010555T patent/DE60010555T2/en not_active Expired - Fee Related
- 2000-03-13 US US09/524,160 patent/US6733552B1/en not_active Expired - Lifetime
- 2000-03-13 EP EP00302007A patent/EP1036757B1/en not_active Expired - Lifetime
- 2000-03-15 CN CN00104316.1A patent/CN1189386C/en not_active Expired - Fee Related
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100393608C (en) * | 2002-08-20 | 2008-06-11 | 千年电池公司 | System for hydrogen generation |
| CN107098310A (en) * | 2016-02-23 | 2017-08-29 | 苏州芷宁信息科技有限公司 | A kind of continuous hydrogen-feeding system |
Also Published As
| Publication number | Publication date |
|---|---|
| DE60010555T2 (en) | 2005-05-12 |
| EP1036757B1 (en) | 2004-05-12 |
| US6733552B1 (en) | 2004-05-11 |
| CN1189386C (en) | 2005-02-16 |
| EP1036757A1 (en) | 2000-09-20 |
| DE60010555D1 (en) | 2004-06-17 |
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